Process and apparatus for recovering components of sealed type battery

ABSTRACT

A recovering process for recovering the constituent components of a sealed type batter comprising at least an a cathode, an anode and an electrolyte sealed in a battery housing, characterized in that said process includes a step (a) of decreasing the ionic conductivity between said cathode and anode of said sealed type battery and a step (b) of opening said battery housing of the sealed type battery after conducting said step (a). An apparatus suitable for practicing said recovering process.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a process and apparatus forrecovering the constituent components of a sealed type battery. Moreparticularly, the present invention relates to a process and apparatusfor safely and efficiently opening a sealed type battery to recover theconstituent components thereof.

[0003] 2. Related Background Art

[0004] In recent years, global warming from the so-called greenhouseeffect has been predicted due to increased level of atmospheric CO₂. Toprevent this warming phenomenon from further developing, there is atendency to prohibit the construction of new steam-power generationplants which exhaust a large quantity of CO₂.

[0005] Under these circumstances, proposals have been made to instituteload leveling in order to effectively utilize power. Load levelinginvolves the installation of rechargeable batteries at general locationsto serve a storage for surplus power unused in the night, known as dumppower. The power thus stored is available in the day time when the powerdemand is increased, leveling the load requirements in terms of powergeneration.

[0006] Separately, there is an increased societal demand for developinga high performance rechargeable battery with a high energy density foran electric vehicle which would not exhaust air polluting substances.There is further increased societal demand for developing a miniature,lightweight, high performance rechargeable battery usable as a powersource for potable instruments such as small personal computers, wordprocessors, video cameras, and pocket telephones.

[0007] For the batteries including rechargeable batteries for such usesas above mentioned, there have been developed various storage batteriesincluding rechargeable batteries having an enclosed (or sealed)configuration. Specific examples of such storage battery are lead-acidbattery, nickel-cadmium battery, nickel-metal hydide battery having ahigh energy density, nickel-zinc battery, rechargeable lithium batteryand like others. In order for these storage batteries to have a longbattery lifetime or/and to be ensured in terms of safety, there isusually employed a sealing manner with the use of a battery housing. Inaddition, in order to ensure further safety, these batteries are mostlyprovided with a safety vent. This safety vent serves to ensure thesafety when the inside pressure of the battery housing is incidentallyincreased, by communicating the inside of the battery housing to theatmosphere outside the battery housing to thereby reduce the increasedinside pressure of the battery housing.

[0008] Now, the nickel-metal hydide battery is a rechargeable battery inwhich electrochemical oxidation-reduction reaction of hydrogen ion isused. The nickel-metal hydride battery typically comprises an anodecomprising an anode active material layer comprised of a hydrogenstorage (absorbing) alloy, a cathode comprising a cathode activematerial layer comprised of nickel hydroxide (specifically, nickeloushydroxide), and an electrolyte solution. In this battery, when chargingis operated, the hydrogen ion of the electrolyte solution at the side ofthe anode is reduced into hydrogen, followed by entering into the anodeactive material layer of the anode where the hydrogen is retainedtherein, and when discharging is operated, the hydrogen retained in theanode active material layer is oxidized into hydrogen ion, followed byincorporating into the electrolyte solution. For the cathode activematerial layer of the cathode, the constituent nickel oxyhydroxide isoxidized into a nickel oxide when charging is operated, and whendischarging is operated, the nickel oxyhydroxide is reduced into theoriginal nickel hydroxide. For the nickel-metal hydride battery, inorder for the hydrogen storage alloy of the anode to efficiently retainhydrogen upon operating the charging and also in order to attain a highbattery capacity, the components of the battery are usually sealed in abattery housing.

[0009] There are known various lithium batteries in whichelectrochemical oxidation-reduction reaction of lithium ion is used. Inthese lithium batteries, because lithium is readily reacted withmoisture in the atmosphere to cause a decrease in the battery capacity,there are used an electrolyte solution in which a nonaqueous organic orinorganic solvent which is substantially free of moisture is used, and abattery housing capable of sufficiently sealing their components. Andthe fabrication of these batteries is conducted in an atmosphere whichis sufficiently free of moisture.

[0010] Specific examples of these lithium batteries, there can beillustrated commercially available primary lithium batteries,commercially available so-called lithium ion batteries, and rechargeablelithium metal batteries (which have been put into the research or whichare under development). In the primary lithium battery and rechargeablelithium metal batteries, their anodes have an anode active materiallayer comprising a lithium metal.

[0011] In the lithium ion battery, as the anode active material layer,there is used a carbonous material such as graphite capable ofintercalating lithium ion into the network planes of the carbonousmaterial when charging is operated, and as the cathode, there is used atransition metal compound capable of intercalating lithium ion into thetransition metal compound when discharging is operated.

[0012] Incidentally, the foregoing storage batteries includingrechargeable batteries enclosed by such battery housing as abovedescribed have been currently using in various potable instruments. Forthese sealed type batteries, to recover them and to recycle theircomponents will be essential not only in terms of development of newpotable instruments but also in viewpoints that they are expected to befurther developed in the future so that they can be used in electricvehicles, load conditioners, power storage, or the like, and also in aviewpoint that the consumption of the batteries is expected to greatlyincrease in the future.

[0013] However, in order to recover the components of these sealed typebatteries, it is necessary to firstly open their battery housings. Inthis case, problems are liable to entail in that upon the opening, thecathode is often contacted with the anode to cause internal shortsbetween the two electrodes, where the residual electric capacity issuddenly consumed within a short period of time to cause heatgeneration, resulting in deteriorating the battery components such thatthey cannot be recycled. Because of this, there cannot be attained adesirable recovery for the battery components.

[0014] In this respect, for the sealed type batteries, there is anincreased demand for developing a recovering process including a openingprocess which enables to efficiently recover their components withoutbeing damaged or deteriorated even in the case where their cathode andanode are contacted with each other upon the opening.

SUMMARY OF THE INVENTION

[0015] The present invention has been accomplished in view of theforegoing situation in the prior art.

[0016] An object of the present invention is to provide a recoveringprocess which enables to safely and efficiently recover the componentsof a sealed type battery without the components being damaged ordeteriorated.

[0017] Another object of the present invention is to provide arecovering apparatus which enables to safely and efficiently recover thecomponents of a sealed type battery without the components being damagedor deteriorated.

[0018] A first aspect of the present invention lies in a recoveringprocess for recovering the components of a sealed type battery sealed,comprising at least a step of decreasing the ionic conductivity betweenthe cathode and anode and a step of opening the battery housing.

[0019] A second aspect of the present invention lies in a recoveringapparatus for recovering the components of a sealed type battery,comprising at least a means for decreasing the ionic conductivitybetween the cathode and anode and a means for opening the batteryhousing.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020]FIG. 1 is a schematic flow diagram illustrating an example of therecovering process for recovering the components of an sealed typebattery according to the present invention.

[0021]FIG. 2 is a schematic flow diagram illustrating another example ofthe recovering process for recovering the components of a sealed typebattery according to the present invention.

[0022]FIG. 3 is a schematic diagram illustrating the constitution of anexample of an apparatus suitable for extracting an electrolyte solutionor a solvent thereof present in a sealed type battery to decrease theionic conductivity between the cathode and anode in the sealed typebattery prior to opening the sealed type battery, which is used as apart of the recovering apparatus according to the present invention.

[0023]FIG. 4 is a schematic diagram illustrating the constitution ofanother example of an apparatus for extracting an electrolyte solutionor a solvent thereof present in a sealed type battery to decrease theionic conductivity between the cathode and anode in the sealed typebattery prior to opening the enclosed battery, which is used as a partof the recovering apparatus according to the present invention.

[0024]FIG. 5 is a schematic conceptual view illustrating an apparatusportion as a principal portion of the recovering apparatus according tothe present invention, comprising a cooling means and an unsealing(opening) means.

[0025]FIG. 6 is a schematic diagram of an example of a cooling meansused in the recovering apparatus according to the present invention.

[0026]FIG. 7 is a schematic cross-sectional view illustrating an exampleof a sealed type battery whose components are recovered in the presentinvention.

[0027]FIG. 8 is a schematic cross-sectional view illustrating an exampleof a coin-like shaped battery.

[0028]FIG. 9 is a schematic cross-sectional view illustrating an exampleof a spiral-wound cylindrical battery.

[0029]FIG. 10 is a schematic perspective view illustrating an example ofa prismatic battery.

DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

[0030] As previously described, the present invention includes arecovering process for recovering the components of a sealed typebattery sealed, comprising at least a step of decreasing the ionicconductivity between the cathode and anode and a step of opening thebattery housing; and a recovering apparatus for recovering thecomponents of a sealed type battery, comprising at least a means fordecreasing the ionic conductivity between the cathode and anode and ameans for opening the battery housing.

[0031] A principal feature of the recovering process is that prior toopening the sealed type battery, to decrease the ionic conductivitybetween the cathode and anode is conducted. Similarly, a principalfeature of the recovering apparatus according to the present inventionis to have a specific means for decreasing the ionic conductivitybetween the cathode and anode prior to opening the enclosed typebattery.

[0032] In the present invention, by extracting the electrolyte solutionor the solvent of the electrolyte solution outside the sealed typebattery to decrease the ionic conductivity between the cathode and anodeprior to opening the battery housing of the sealed type battery, even inthe case where internal shorts should be occurred between the cathodeand anode when the battery housing is opened or the battery componentsare taken out from the inside of the battery housing as will bedescribed later, the occurrence of sudden energy release and combustiondue to the internal shorts is effectively prevented. As a result, it ispossible to safely recover the battery components without beingdeteriorated or destroyed. By this, there can be realized safe recoveryof the components of the sealed type battery at a high recovery rate.

[0033] The recovering process and apparatus according to the presentinvention are effective in recovering the components of any sealed typebatteries including sealed type primary and secondary (rechargeable)batteries, notwithstanding the kind of a battery enclosed therein.

[0034] Specific examples of such sealed type battery for which therecovering process and the recovering apparatus according to the presentinvention are particularly effective in recovering the batterycomponents are lithium batteries including lithium ion rechargeablebatteries (in which an anode comprising a carbonous material capable ofintercalating lithium ion is used) in which electrochemicaloxidation-reduction reaction of lithium ion is used; nickel-metalhydride rechargeable batteries having an anode comprising a hydrogenstorage alloy and in which electrochemical oxidation-reduction reactionof hydrogen ion is used; and nickel-cadmium batteries.

[0035] Herein, for the lithium batteries, a variety of enclosed typeprimary lithium batteries having an anode comprising a lithium metalhave been frequently using in potable instruments such as cameras,wristwatches and the like. And the consumption of these primary lithiumbatteries are expected to further increase in the future. In addition,the consumption of rechargeable lithium batteries is expected toincrease in the future. Under this circumstance, the waste disposal ofthese lithium batteries will be possibly a serious problem in the futureas well as in the case of other batteries. In this respect, it is anurgent necessity of recovering and recycling their components such asanodes, cathodes, electrolytes, separators, and housings.

[0036] Now, in order to separately recover the components of an usedsealed type lithium battery, the battery housing is required to beopened while preventing external moisture invasion, which will be acause of damaging or deteriorating the battery characteristics.

[0037] As a most simple manner for unsealing the battery housing of anenclosed type battery, there is considered a mechanically cuttingmanner. However, when this manner is employed particularly in the caseof an enclosed type lithium battery, problems are liable to entail inthat as the energy per unit volume and unit weight is extremely high anda combustible material such as organic solvent is contained, a spark isgenerated or internal shorts are occurred between the anode and cathodeupon mechanically cutting the battery housing, where the components aredamaged or deteriorated. Besides, other problems are liable to entailsuch that will be described in the following. When the batterycomponents situated inside the battery housing are taken out after thebattery housing has been unsealed, as the anode and cathode are closedto each other, they tend to readily suffer from internal shorts wherethe internal shorts should be occurred between them, the residualbattery energy is released at a stroke to cause sudden heat generation.

[0038] Therefore, particularly for a sealed type lithium battery, thereis demand for developing a desirable recovering process and a desirablerecovering apparatus capable of recovering the battery componentswithout being damaged or deteriorated for dealing with an increase inthe consumption thereof.

[0039] The present invention desirably meets this demand.

[0040] In the recovering process for recovering the components of asealed type battery which comprises an electrolyte solution as theelectrolyte, the step of decreasing the ionic conductivity between thecathode and anode is desired to be conducted by a manner of extractingthe electrolyte solution or the solvent thereof present within thebattery housing outside the battery housing. In the case where theenclosed battery provided with a safety vent, to extract the electrolytesolution or the solvent thereof outside the battery housing is desiredto be conducted while taking advantage of the safety vent in view ofworking efficiency, for instance, in a manner wherein through the safetyvent, the pressure of the atmosphere outside the battery housing isdecreased to increase the inside pressure of the battery housing wherebycausing a differential pressure between the outside and the inside ofthe battery housing, and by this, the safety vent is actuated to extractthe electrolyte solution or the solvent thereof outside the batteryhousing. The electrolyte solution or the solvent thereof thus extractedoutside the battery housing can be recycled.

[0041] In the recovering process for recovering the components of asealed type battery, the step of decreasing the ionic conductivitybetween the cathode and anode is desired to be conducted at leastthrough a manner of cooling the enclosed type battery. In the case wherethis manner is employed, when a solvent is used in the electrolytesolution of the sealed type battery, it is desired to cool the sealedtype battery to a temperature which is lower than the freezing point ofthe solvent. In the case where a solid polymer electrolyte solidified byusing a polymer is used in the sealed type battery, it is desired tocool the sealed type battery to a temperature which is lower than theglass transition temperature of the constituent polymer of the solidpolymer electrolyte.

[0042] The above manner of cooling the sealed battery can be conductedby a cooling manner of cooling an object using an incombustiblecompressed gas comprising one or more gases selected from the groupconsisting of N₂ gas, Ar gas, He gas, CO₂ gas and fluorocarbon gas.

[0043] Besides this, it is possible for the above manner of cooling thesealed type battery to be conducted by a manner of cooling the sealedtype battery by immersing it in a cooling agent or a liquefied gas. Thecooling agent can include, for example, a mixture comprising dryice andmethanol and a mixture comprising dryice and ethanol. The liquefied gascan include, for example, liquid nitrogen and the like.

[0044] Alternatively, it is possible for the above manner of cooling thesealed type battery to be conducted by a manner of immersing the sealedtype battery in water, followed by freezing the enclosed type batterytogether with the water. In this case, the sealed type battery isdesired to be opened in a state in that the sealed type battery issealed in the ice.

[0045] In the recovering process for recovering the components of asealed type battery, it is desired for the step of opening the batteryhousing after the ionic conductivity between the cathode and anode hasbeen decreased to be conducted in an incombustible atmosphere. In thiscase, there are provided advantages in that the battery components areprevented from being oxidized or combusted and they can be safelyrecovered while desirably preventing them from being damaged ordeteriorated at a high recovery. The above incombustible atmosphere maybe an atmosphere composed of one or more gases selected from the groupconsisting of N₂ gas, Ar gas, He gas, CO₂ gas, fluorocarbon gas, andsteam. In the case where the foregoing cooling manner using theincombustible compressed gas is employed in the step of decreasing theionic conductivity between the cathode and anode, the gas used toconstitute the atmosphere for opening the battery housing is desired tothe same as the gas used as the compressed gas.

[0046] As the manner of opening the battery housing, there can beillustrated a cutting process using a high pressure water, a cuttingprocess using a energy beam, a mechanically cutting process, and acutting process by way of spraying a high pressure water containing anabrasive mixed therein to an object through a jet nozzle.

[0047] In the present invention, by subjecting the battery todischarging prior to opening the housing of the sealed type battery,preferably at a stage before decreasing the ionic conductivity betweenthe cathode and anode, to open the sealed type battery can be moresafely conducted. In this case, the chemical composition of theconstituent material for each of the cathode and anode active materiallayers becomes uniform without depending upon the residual batterycapacity before the discharging, where the cathode material and theanode material each having a satisfactory uniformity in terms of thechemical composition can be recovered. Further in this case, by means ofthe discharging, it is possible to withdraw the energy remained in theenclosed battery.

[0048] Further in the present invention, by sorting the sealed batteriesdepending on the shape or the type before their housings are unsealed,their components can be efficiently recovered.

[0049] As previously described, the recovering apparatus according tothe present invention for recovering the components of a sealed typebattery sealed by a battery housing, comprises at least a means fordecreasing the ionic conductivity between the cathode and anode and ameans for opening the battery housing.

[0050] The means for decreasing the ionic conductivity between thecathode and anode is desired to comprise at least a means for extractingthe electrolyte solution or the solvent thereof present inside thebattery housing outside the battery housing. In the case where thesealed type battery is provided with a safety vent, this means isdesired to have a function of actuating the safety vent, for instance,by decreasing the pressure of the atmosphere outside battery housing toincrease the inside pressure of the battery housing across the safetyvent whereby causing a differential pressure between the outside and theinside of the battery housing and a means for extracting the electrolytesolution or the solvent thereof present inside the battery housingoutside the battery housing through the safety vent. The means forextracting the electrolyte solution or the solvent thereof presentinside the battery housing outside the battery housing is desired tocomprise a vessel provided with at least an exhaust means. It is desiredfor the vessel in this case to be provided with a member which can beclose-contacted with or joined to the battery housing's exterior wallface including a portion of the battery capping in the neighborhood ofthe safety vent and an opening (or a passage) for transferring theelectrolyte solution or the solvent thereof (which is extracted from thebattery) into the vessel.

[0051] In the above described vessel, a port capable of introducing air,nitrogen gas (N₂) or inert gas thereinto may be provided through avalve.

[0052] In the recovering apparatus according to the present invention,for instance, by establishing a closed or sealed space by a part of thebattery housing's exterior face including the battery capping or theentire thereof (including the portion through which the electrolytesolution or the solvent thereof is extracted) and the above describedvessel and decreasing the inner pressure of the sealed space than theinner pressure of the enclosed battery while maintaining the safety ventportion in the sealed space, the electrolyte solution or the solventpresent inside the battery housing can be desirably recovered into thevessel through the safety vent.

[0053] In the recovering apparatus according to the present invention,the above closed (sealed) space is desired to be established byconnecting the above vessel provided with the exhaust means to a regionincluding a portion (e.g., the safety vent) through which theelectrolyte solution or the solvent thereof present inside the batteryhousing is extracted after the inner pressure of the above vessel hasbeen decreased than the atmospheric pressure by means of the exhaustmeans provided at the vessel.

[0054] In the recovering apparatus according to the present invention,it is possible that the above closed space is first established by theabove and thereafter, the inner pressure of the sealed space is loweredthan the inner pressure of the sealed battery by means of the aboveexhaust means provided at the vessel.

[0055] In the recovering apparatus according to the present invention,the foregoing means for decreasing the ionic conductivity between thecathode and anode is desired to comprise a cooling means for cooling thesealed type battery.

[0056] To cool the sealed type battery by means of the cooling means isdesired to be conducted by using an incombustible compressed gascomprising one or more gases selected from the group consisting of N₂gas, Ar gas, He gas, CO₂ gas and fluorocarbon gas in the cooling means.

[0057] Alternatively, to cool the enclosed battery by means of thecooling means may be conducted by using a cooling agent or a liquefiedgas in the cooling means. The cooling agent can include, for example, amixture comprising dryice and methanol and a mixture comprising dryiceand ethanol. The liquefied gas can include, for example, liquid nitrogenand the like.

[0058] Further, it is possible that the sealed type battery is immersedin water, followed by freezing the sealed type battery together with thewater. In this case, the sealed type battery is desired to be opened ina state in that the enclosed battery is sealed in the ice.

[0059] In the recovering apparatus according to the present invention,as the means for unsealing the battery housing, there can be illustrateda cutting means using a high pressure water, a cutting means using aenergy beam, a mechanically cutting means, and a cutting means using ahigh pressure water containing an abrasive mixed therein.

[0060] To open the battery housing by any of these cutting means isdesired to be conducted in an incombustible atmosphere. Theincombustible atmosphere may be an atmosphere composed of one or moregases selected from the group consisting of N₂ gas, Ar gas, He gas, CO₂gas, fluorocarbon gas, and steam.

[0061] In the following, preferred embodiments of the present inventionwill be described while referring to the drawings.

[0062]FIG. 1 is a schematic flow diagram illustrating an example of therecovering process for recovering the components of a sealed typebattery according to the present invention.

[0063] Description will be made of an embodiment of the recoveringprocess according to the present invention with reference to FIG. 1.

[0064] In order to efficiently recover the components of a sealed typebattery, used sealed type batteries (FIG. 1(a-1)) collected forrecovering their components are first sorted depending on the shape orthe type (see, FIG. 1(a-2)).

[0065] Then, the sealed type battery thus sorted is subjected todecrease the ionic conductivity between the anode and cathode (see, FIG.1(a-3)). In this case, to decrease the ionic conductivity between thecathode and anode may be conducted by the foregoing manner of extractingthe electrolyte solution or the solvent thereof present between thecathode and anode (in the case of using the electrolyte solution as theelectrolyte in the battery) outside the battery housing through thesafety bent or the like annexed to the battery housing. Alternatively,it may be conducted by the foregoing manner of cooling the battery todecrease the ionic conductivity between the cathode and anode.

[0066] Thereafter, the battery housing is opened (see, FIG. 1(a-4)),followed by taking out a body comprising the battery components presentinside the battery housing (see, FIG. 1(a-5)).

[0067] The body thus taken out is washed (see, FIG. 1(a-6). Then, thebody is dissociated (separated) into individual battery components andthe battery components thus dissociated are recovered (see, FIG.1(a-7)).

[0068]FIG. 2 is a schematic flow diagram illustrating another example ofthe recovering process for recovering the components of a sealed typebattery according to the present invention.

[0069] Description will be made of another embodiment of the recoveringprocess according to the present invention with reference to FIG. 2.

[0070] In order to efficiently recover the components of each usedsealed type battery, used sealed type batteries (FIG. 2(b-1)) collectedfor recovering their components are first sorted depending on the shapeor the type (see, FIG. 2(b-2)).

[0071] Then, the sealed type battery thus sorted is cooled to decreasethe ionic conductivity between the anode and cathode whereby increasingthe internal resistance (see, FIG. 2(b-3)).

[0072] Thereafter, the battery housing of the sealed type battery thuscooled in the above step is opened in an incombustible atmosphere (see,FIG. 2(b-4)).

[0073] Then, in the case where the battery in the sealed type battery isbased on a lithium battery, an appropriate reacting agent is reactedwith the active lithium present inside the battery housing to decreasethe reactivity of the lithium (see, FIG. 2(b-5)).

[0074] Successively, a body comprising the battery components presentinside the battery housing is taken out (see, FIG. 2(b-6)).

[0075] In the case where the electrolyte is in the liquid state, thebody (comprising the battery components) thus taken out is washed withan appropriate organic solvent (see, FIG. 2(b-7)).

[0076] Then, the body thus washed is dissociated into individual batterycomponents and the battery components thus dissociated are recovered(see, FIG. 2(b-8)).

[0077] If necessary, the residual electric capacity in the used sealedbattery may be discharged after sorting the battery, where the steps ofopening the battery housing, dissociating the battery into individualcomponents and recovering the components may be conducted more safely.Specific examples of the manner for doing this, there can be mentioned amanner wherein the anode and cathode terminals of the battery areelectrically connected to a capacitor to conduct discharging, and amanner wherein charging is conducted by connecting a resistance betweenthe anode and cathode terminals of the battery. In any case, thecharging is conducted until the electric capacity of the batterydecreases suddenly.

[0078] In the following, with reference to the drawings, descriptionwill be made of the foregoing manner of extracting the electrolyte orthe solvent thereof present inside the battery housing as a measure fordecreasing the ionic conductivity between the cathode and anode in asealed type battery.

[0079]FIG. 3 is a schematic diagram illustrating the constitution of anexample of an apparatus suitable for extracting an electrolyte solutionor a solvent thereof present in a sealed type battery to decrease theionic conductivity between the cathode and anode in the sealed typebattery prior to opening the housing of the sealed type battery, whichis used as a part of the recovering apparatus according to the presentinvention.

[0080]FIG. 4 is a schematic diagram illustrating the constitution ofanother example of an apparatus suitable for extracting an electrolytesolution or a solvent thereof present in a sealed type battery todecrease the ionic conductivity between the cathode and anode in thesealed type battery prior to opening the housing of the sealed typebattery, which is used as a part of the recovering apparatus accordingto the present invention.

[0081] Each of the apparatus shown in FIGS. 3 and 4 is corresponding toan example of a system used in the foregoing recovering apparatus, forextracting the electrolyte solution or the solvent thereof through thesafety vent or the like to decrease the ionic conductivity between thecathode and anode in the sealed type battery prior to opening thehousing of the sealed type battery while recovering the electrolytesolution or the solvent thereof.

[0082] In the case of the apparatus shown in FIG. 3, the apparatus iscontacted through its specific contact means with a sealed type batteryhaving a safety vent such that the apparatus is tightly contacted with aportion of the battery housing's exterior wall of the sealed typebattery in the neighborhood of the safety vent and the neighborhood ofthe safety vent is locally depressurized to cause a differentialpressure between the outside and the inside of the battery housing. Bythis, the safety vent is actuated to communicate the outside and theinside of the battery housing whereby the electrolyte or the solventthereof present inside the battery housing is extracted.

[0083] In the case of the apparatus shown in FIG. 4, the apparatus isprovided with a specific vessel capable of being vacuumed. An enclosedtype battery is placed in the vessel, and the inside (containing theenclosed type battery) of the vessel is depressurized to relativelyincrease the internal pressure of the sealed type battery wherebycausing a differential pressure between the outside and the inside ofthe battery housing. By this, the safety vent is actuated to communicatethe outside and the inside of the battery housing whereby theelectrolyte or the solvent thereof present inside the battery housing isextracted.

[0084] Description will be made of the apparatus shown in FIG. 3 and itsoperation.

[0085] In FIG. 3, reference numeral 100 indicates an enclosed typebattery sealed in a battery housing 101. Reference numeral 102 indicatesa safety bent annexed to the enclosed type battery.

[0086] Reference numeral 103 indicates an extraction pipe for extractingan electrolyte solution or a solvent of said electrolyte solution fromthe battery 100. The extraction pipe 103 is provided with a switchingvalve 108 serving as an extraction valve for an electrolyte or a solventof said electrolyte solution, and it is also provided with a gas supplypipe for introducing air, nitrogen gas or inert gas into the apparatus.The gas supply pipe is provided with a leak valve 113.

[0087] Reference numeral 104 indicates a storage tank for storing theelectrolyte solution or the solvent thereof extracted from the enclosedtype battery 100 through the extraction pipe 103.

[0088] Reference numeral 105 indicates a vacuuming means comprising avacuum pump or the like which is connected to the storage tank 104through an exhaust pipe 107 provided with an exhaust valve 109.Reference numeral 106 indicates an O-ring for attaining a tight contact.Reference numeral 110 indicates a drain valve provided at the storagetank 104.

[0089] Particularly, in the apparatus shown in FIG. 3, the extractionpipe 103 has a first opening portion provided with the O-ring 106, asecond opening portion open into the storage tank 104, and a gasintroduction opening portion through which air, nitrogen gas orincombustible gas supplied through the gas supply pipe provided with theleak valve 113 can be introduced into the inside of the apparatus. Saidfirst opening portion is situated at an exterior wall portion of thebattery housing 101, said exterior wall portion including theneighborhood of the safety vent 102 of the sealed battery 100, and saidneighborhood including a portion of a battery capping or lid (not shown)of the battery 100. Particularly, the first opening portion is tightlycontacted with or joined to said exterior wall portion of the batteryhousing 101 through the O-ring 106 as shown in FIG. 3. And as abovedescribed, the second opening portion of the extraction pipe 103 is openinto the storage tank 104. By this, the battery 100 is communicated withthe inside of the storage tank 104 through the extraction pipe 103.

[0090] In the above system, there is established a space comprising theabove described battery housing's exterior wall portion (including thesafety vent 102 of the battery 100), the inside of the extraction pipe103 and the inside of the storage tank 104. Herein, the battery 100 isarranged such that its portion having the safety vent 102 downwardlyfaces as shown in FIG. 3. By means of the vacuuming means 105 connectedthrough the exhaust pipe 107 provided with the exhaust valve 109 to thestorage tank 104, the inside of the system is depressurized to make theabove space have an internal pressure which is lower than that of thebattery 100. By this, the safety vent 102 is actuated (opened in otherwords), where the electrolyte solution or the solvent thereof containedin the battery 100 is extracted into the extraction pipe 103, followedby flowing into the storage tank 104. As a result, there is provided asituation in that no electrolyte solution is present between the cathodeand anode (not shown) in the battery 100 and the ionic conductivitybetween the two electrodes is decreased.

[0091] In the above operation, if necessary, it is possible that theleak valve 113 of the gas supply pipe is actuated to introduce air,nitrogen gas or inert gas into the system.

[0092] For the electrolyte solution or the solvent thereof extractedinto the storage tank 104, a predetermined amount thereof isperiodically drained by actuating the drain valve 110 to the outside,followed by recovering. The electrolyte solution or the solvent thereofthus recovered may be recycled.

[0093] In the following, description will be made of the apparatus shownin FIG. 4 and its operation.

[0094] The apparatus shown in FIG. 4 comprises a battery container 111provided with a extraction pipe 103 which is extended into a storagetank 104. The battery container 111 serves to house a sealed typebattery 100 having a safety vent 102 to be treated. The extraction pipe103 serves to extract an electrolyte solution or a solvent of saidelectrolyte solution contained in the sealed type battery 100. Theextraction pipe 103 has an opening at one end thereof which is open intothe battery container 111 and another opening at the other end thereofwhich is open into the storage tank 104. The extraction pipe 103 isprovided with a switching valve 108 serving as an extraction valve forthe electrolyte solution or the solvent thereof.

[0095] The storage tank 104 serves to store the electrolyte solution orthe solvent thereof which is extracted from the battery 100 through theextraction pipe 103. The inside of the storage tank 104 is connected toa vacuuming means 105 comprising a vacuum pump or the like through anexhaust pipe 107 provided with an exhaust valve 109.

[0096] The battery container is provided with a gas supply pipe providedwith a leak valve 113, which serves to introduce air, nitrogen gas orinert gas into the battery container 111. Reference numeral 112indicates a capping for the battery container 111. The capping 112 istightly capped to the battery container 111 by means of an O-ring 106.

[0097] In the above system, there is established a space comprising thecapping 112, the inside of the battery container 111, the entire of thebattery housing's exterior wall including the safety vent 102, theinside of the extraction pipe 103 and the inside of the storage tank104. Herein, the battery 100 is arranged such that its portion havingthe safety vent 102 downwardly faces as shown in FIG. 4. By means of thevacuuming means 105, the inside of the system (from the extraction pipe103 through the storage tank) is depressurized to make the above spacehave an internal pressure which is lower than that of the battery 100.By this, the safety vent 102 is actuated (opened in other words), wherethe electrolyte solution or the solvent thereof contained in the battery100 is extracted into the extraction pipe 103, followed by flowing intothe storage tank 104. As a result, there is provided a situation in thatno electrolyte solution is present between the cathode and anode (notshown) in the battery 100 and the ionic conductivity between the twoelectrodes is decreased.

[0098] In the above operation, if necessary, it is possible that theleak valve 113 of the gas supply pipe is actuated to introduce air,nitrogen gas or inert gas into the system.

[0099] For the electrolyte solution or the solvent thereof extractedinto the storage tank 104, a predetermined amount thereof isperiodically drained by opening the drain valve 110 to the outside,followed by recovering. The electrolyte solution or the solvent thereofthus recovered may be recycled.

[0100] For the sealed type battery from which the electrolyte solutionor the solvent thereof has been extracted in the system shown in FIG. 3or 4 as above described, its housing is opened by an appropriateunsealing manner in a state in that the ionic conductivity between thecathode and anode has been decreased, and the battery components arerecovered.

[0101] In the following, description will be made of an embodiment ofthe step of increasing the internal resistance of a sealed type batteryby cooling the battery and an embodiment of the step of opening thehousing of said cooled battery in the process for recovering thecomponents of a sealed type battery by decreasing the ionic conductivitybetween the cathode and anode in the sealed type battery, whilereferring to an apparatus shown in FIG. having a system capable ofconducting these steps.

[0102]FIG. 5 is a schematic conceptional view illustrating an example ofan apparatus for cooling a sealed type battery and opening its batteryhousing as a part of the recovering apparatus according to the presentinvention for recovering the components of a sealed type battery.

[0103] In the apparatus shown in FIG. 5, there is shown a case wherein acooling apparatus capable of cooling a sealed type battery by using acompressed gas of an incombustible gas is used, and the sameincombustible gas is used as an atmosphere under which to unseal thebattery housing is conducted. The apparatus shown in FIG. 5 is providedwith a means for recovering the gas having used for cooling the enclosedtype battery, purifying the recovered gas and recycling the purifiedgas. In the apparatus shown in FIG. 5, in order to open the batteryhousing, a high pressure water or energy beam is used.

[0104] The apparatus shown in FIG. 5 and its operation will be detailed.

[0105] In FIG. 5, reference numeral 200 indicates an enclosed typebattery, reference numeral 201 a cooling apparatus (a low temperaturegas-blowing apparatus), reference numeral 202 a low temperature gas,reference numeral 203 an incombustible atmosphere, reference numeral 204an unsealing apparatus for a battery housing, reference numeral 205 ahigh pressure water or energy beam, reference numeral 206 a partitionwall, reference numeral 207 a fixing table for an enclosed type battery,reference numeral 208 a transportation mechanism for an enclosed typebattery, reference numeral 209 a gas feed pipe for a compressed gas,reference numeral 210 a compressor, reference numeral 211 a removingdevice for removing impurities such as water, reference numeral 212 anincombustible gas-recovering device, reference numeral 213 a gas pipefor recovering an incombustible gas, reference numeral 214 a generationdevice for generating a high pressure water or energy beam, andreference numeral 215 a transfer pipe for a high pressure water or atransmission pipe for an energy beam.

[0106] In the apparatus shown in FIG. 5, a used, sealed type battery 200is fixed onto the fixing table 207 arranged on transportation mechanism208 provided in the chamber demarcated by the partition wall 206,followed by sequentially transporting to the cooling step zone havingthe cooling apparatus 201 then to the unsealing step zone having theunsealing apparatus 204. The chamber space demarcated by the partitionwall 206 including the zone of the cooling apparatus 201 and the zone ofthe unsealing apparatus is filled with an incombustible gas (theincombustible atmosphere 203).

[0107] At the cooling apparatus 201, a low temperature gas 202comprising a cooled incombustible gas is supplied to the enclosed typebattery 200 to cool the electrolyte contained in the enclosed batterywhereby decrease its ionic conductivity. As the low temperature gas 202used herein, it is desired that the incombustible gas inside thepartition wall 206 is recycled to use. Particularly in this respect,said incombustible gas is recovered by the incombustible gas-recoveringdevice 212 through the gas conduit 213 connected to the chamberdemarcated by the partition wall 206, purified by theimpurities-removing device 211, compressed by the compressor 210,supplied to the cooling apparatus 201, followed by supplying to theenclosed type battery 200 as the low temperature gas 202 (the compressedgas).

[0108] In the above cooling step for cooling the enclosed type battery,it is possible to cool the sealed type battery, for example, by using acooling agent or liquefied gas. Alternatively, to cool the sealed typebattery may be conducted by a manner wherein the sealed type battery isimmersed in water, followed by freezing the water together with thebattery such that the battery is sealed in the ice.

[0109] Then, at the unsealing apparatus 204, for example, a highpressure water or energy beam 205 is effected to the sealed type battery200 having been cooled in the above cooling step to open the batteryhousing. The high pressure water or energy beam used herein is producedby the generation device 214, followed by supplying to the unsealingapparatus 204 through the transfer pipe or transmission pipe 215.

[0110] In the following, description will be made of detailed conditionsin the cooling step for cooling an enclosed type battery, said coolingstep including the foregoing cooling step using the apparatus shown inFIG. 5.

Cooling Temperature

[0111] Description will be made of the cooling temperature to which anenclosed type battery is cooled in order to decrease the ionicconductivity of the electrolyte.

[0112] For instance, when the sealed type battery is a sealed typelithium battery in which an electrolyte solution comprising anelectrolyte and an organic solvent is used as the electrolyte, in orderto decrease the ionic conductivity of the electrolyte, the lithiumbattery is desired to be cooled to a temperature which is lower than thefreesing temperature of the organic solvent of the electrolyte solution.

[0113] When the electrolyte of the lithium battery comprises a polymersolid electrolyte solidified by using a polymer, in order to decreasethe ionic conductivity of the electrolyte, the lithium battery isdesired to be cooled to a temperature which is lower than the glasstransition temperature of the polymer of the polymer solid electrolyte.

[0114] Specifically, the range of the cooling temperature is preferably0° C. or less, more preferably −20° C. or less.

[0115] In the case where the sealed type battery is other sealed typebattery such as sealed type metal hydride battery, sealed typenickel-cadmium battery, sealed type lead-acid battery, or the like, thecooling temperature for these batteries is desired to be in the abovedescribed temperature range.

Cooling Means

[0116] Description will be made of the cooling means for cooling asealed type batter in order to decrease the ionic conductivity of theelectrolyte.

[0117] To cool a sealed type battery in order to decrease the ionicconductivity of the electrolyte may be conducted by a cooling mannerwith the use of a compressed gas comprising an incombustible gas (byusing an appropriate cooling apparatus such as the cooling apparatus 201shown in FIG. 5), or other cooling manner with the use of a liquefiedgas or a cooling agent.

[0118] The cooling manner with the use of a compressed gas comprising anincombustible gas may be conducted also by using a cooling apparatus asshown in FIG. 6. The cooling apparatus shown in FIG. 6 is a tube-likeshaped cooling apparatus comprising a compressed gas supply port 705through which a compressed gas 704 is supplied, a hot gas exhaust port708 including a pressure regulator 706, a cooling gas outlet 702, and avortex generator zone 703 to generate a vortex flow 709. Referencenumeral 701 indicates a direction for a cooling gas to be spouted, andreference numeral 707 a hot gas to be exhausted.

[0119] In the cooling apparatus shown in FIG. 6, by flowing a compressedgas 704 into the inside of the apparatus through the gas supply port705, a cooling gas is spouted in the direction 701 through the coolinggas outlet 702. In the case where a gas having a temperature of about16° C. is supplied at a gas pressure of 3 to 7 Kg/cm through the gassupply port 705, there is obtained a cold gas having a temperature ofabout −10 to about −50° C. The compressed gas used in this apparatus maycomprise an incombustible gas comprising one or more gases selected fromthe group consisting of N₂ gas, Ar gas, He gas, CO₂ gas, andfluorocarbon gas.

[0120] By this, particularly in the case where the cooling step and theopening step for the sealed type battery in an continuous atmosphere(which will be described later), even when internal shorts should beincidentally occurred between the node and cathode upon opening thebattery housing by way of a cutting manner, the generation of a sparkcan be desirably prevented. Further, in the case of an enclosed typebattery having a battery housing capable of being opened by way ofdisassembling without conducting cutting operation or the like, thegeneration of a spark due to internal shorts between the anode andcathode can be desirably prevented at the time when the componentsincluding the electrodes are taken out. Because of this, the recoveryoperation of the battery components can be safely conducted.

[0121] In the case where the cooling step is conducted using a liquefiedgas, there can be employed a cooling manner wherein the entire of ansealed type battery to be opened is directly immersed in an appropriateliquefied gas such as liquid nitrogen, liquid helium or the like or acooling manner wherein a gasified low temperature gas of a liquefied gasis sprayed onto the battery housing of the sealed type battery to beunsealed.

[0122] In the case where the cooling step is conducted using a coolingagent, the cooling agent can include dryice-methanol, dryice-ethanol,and ice.

[0123] As previously described, it is possible that a sealed typebattery is immersed in water, the water is frozen together with thebattery, followed by opening the battery housing in a state in thebattery is sealed in the ice.

Battery Opening

[0124] Description will be made of particulars in the opening step foropening the housing of a sealed type battery in which the ionicconductivity of the electrolyte has been decreased by means of theapparatus shown in FIG. 3 or 4 and in the opening step in the apparatusshown in FIG. 5.

[0125] The atmosphere in which to open the housing of a sealed typebattery is conducted is desired to be comprised of an incombustible gascomprising one or more gases selected from the group consisting of N₂gas, Ar gas, He gas, CO₂ gas, steam, and fluorocarbon gas. In this case,even when internal shorts should be incidentally occurred between theanode and cathode upon opening the battery housing, the generation of aspark is desirably prevented and in addition, the battery components aredesirably prevented from being damaged due to oxidation.

[0126] In the case where the cooling step is conducted by spraying a lowtemperature gas to the sealed type battery as previously described, byusing a gas of the same kind as the low temperature gas as theconstituent of the atmosphere in which the unsealing step is conducted,there are provided advantages such that the operation including recoveryand recycling of the gas can be readily conducted and the running costis reasonable.

[0127] Specific examples of the above fluorocarbon gas aretetrafluoromethane, hexafluoroethane, perfluoropropane,trifluoromethane, monobromotrifluoromethane, dichlorodifluoromethane,and chlorotrifluoromethane.

Battery Unsealing Means

[0128] As previously described, to open the battery housing of a sealedtype batter may conducted an appropriate unsealing manner by way ofcutting with the use of a high pressure water or an energy beam (forinstance, the unsealing manner using the unsealing apparatus 204 shownin FIG. 5) or a mechanically cutting manner.

[0129] The cutting with the use of a high pressure water may beconducted, for example, by a manner of spraying an extra-high pressurewater of preferably 1000 Kg/cm² or more or more preferably, 3000 Kg/cm²or more onto the battery housing of an enclosed type battery in ajet-like state through a nozzle. In this case, the extra-high pressurewater to be sprayed may contain an appropriate abrasive depending uponthe kind of the constituent of the battery housing.

[0130] The above energy beam can include laser beam, electron beam andthe like.

[0131] The above mechanically cutting manner may be conducted by using acutting apparatus of cutting an object by rotating a disc-like shapedblade (having a hard and sharp edge) at a high speed or by way ofshearing.

[0132] Incidentally, in the case where the sealed type battery is cooledsuch that the battery is sealed in the ice as previously described, toopen the housing of the battery is desired to be conducted whilemaintaining said sealed state.

[0133] For the sealed type battery in which the ionic conductivity ofthe electrolyte has been decreased and whose housing has been opened aspreviously described, the inside of the resultant battery is subjectedwashing or the like, followed by subjecting to classification andseparation, and at a final stage, the constituent components thereof arerecovered.

Decrease of Reactivity of Active Lithium and Recovery of Lithium Element

[0134] In the case where the sealed type battery to be subjected torecover is a sealed type lithium battery, after the battery housing hasbeen opened, by decreasing the reactivity of an active lithium containedin the lithium battery, the successive step for recovering the batterycomponents can be safely conducted. To decrease the reactivity of theactive lithium having a high reactivity may be conducted by a manner ofreacting an appropriate reacting agent with the active lithium. From thereaction product comprising the reacting agent and lithium obtained inthis case, the recovery of lithium element can be easily conducted.

[0135] Specific examples of the reacting agent are water, alcohols,acids, carbon dioxide, and mixtures of two or more of these.

Recovery of Electrolyte Solution

[0136] In the case where the electrolyte solution of a sealed typebattery is extracted by increasing the internal pressure of the enclosedtype battery, for instance, in the manner previously described withreference to FIGS. 3 and 4, followed by opening the battery housing, therecovery of the electrolyte solution can be easily conducted.

[0137] Now, to recover the electrolyte solution in the case where asealed type battery is cooled and the battery housing is opened may beconducted, for example, in the following manner.

[0138] In the case of a sealed type battery in which an aqueouselectrolyte solution is used, after the battery housing is opened, theresultant unsealed battery is subjected to washing with deionized water,the resultant washed solution is filtrated, followed by vaporizingwater, whereby the electrolyte can be recovered.

[0139] In the case of a sealed type battery in which an electrolytesolution comprising an electrolyte dissolved in an organic solvent isused, after the battery housing is unsealed, the resultant unsealedbattery is subjected to washing with an appropriate organic solvent,followed by subjecting to fractional distillation, whereby theelectrolyte solution can be recovered. As the organic solvent in thiscase, when an organic solvent incapable of forming an azeotrope withwater is used, there are provided advantages such that a cutting mannerusing a high pressure water can be employed in cutting the batteryhousing, and as the reacting agent in order to decrease the reactivityof the active lithium, readily obtainable water with a reasonableproduction cost can be used.

[0140] Description will be made of the above organic solvent incapableof forming an azeotrope with water.

[0141] As above described, in the case of an enclosed type lithium, byusing an organic solvent incapable of forming an azeotrope with water inwashing an unsealed lithium battery obtained as a result of havingunsealed the sealed type lithium battery, even when inexpensivedeionized water is used as the reacting agent to decrease the reactivityof the active lithium contained in the lithium battery, the washingorganic solvent can be readily separated from the water by way offractional distillation.

[0142] Specific examples of the foregoing organic solvent incapable offorming an azeotrope with water are methanol, acetone, 1,2-propanediol,dimethyl sulfoxide, butyrolactone, ethylene carbonate, and propylenecarbonate.

[0143] In the following, description will be made of an enclosed typebattery whose constituent components are recovered according to thepresent invention, while referring to the drawings.

[0144]FIG. 7 is a schematic cross-sectional view illustrating an exampleof a sealed type battery whose constituent components are recoveredaccording to the recovering process or apparatus according to thepresent invention.

[0145] The sealed type battery shown in FIG. 7 comprises an anode 301, acathode 302 and a separator 303 including an electrolyte which areenclosed by a battery housing 304. In the case where a solid electrolyteis used as the electrolyte, no separator is occasionally installed.Reference numeral 305 indicates a negative terminal, and referencenumeral 306 indicates a positive terminal.

[0146] For the configuration of the enclosed type battery (particularly,the sealed type rechargeable battery) whose constituent components arerecovered according to the recovering process or apparatus according tothe present invention, it may be in the form of a flat round shape (or acoin-like shape), a cylindrical shape, a prismatic shape, or asheet-like shape. For the battery structure, it includes asingle-layered type, a multi-layered type and a spiral-wound type. Inthe case of a spiral-wound cylindrical battery comprising a stacked body(comprising a separator interposed between an anode and a cathode)wounded in multiple about a predetermined axis, it has advantages inthat the battery area can be increased as desired and a high electriccurrent can be flown upon operating charging and discharging. In thecase of a battery in either a prismatic form or sheet-like form, it hasan advantage in that the space of an instrument for housing the batterycan be effectively utilized.

[0147] In the following, description will be made of the shape andstructure of such a battery with reference to FIGS. 8, 9 and 10.

[0148]FIG. 8 is a schematic cross-sectional view illustrating an exampleof a single-layer structure type flat battery. FIG. 9 is a schematiccross-sectional view illustrating an example of a spiral-woundcylindrical battery. FIG. 10 is a schematic perspective viewillustrating an example of a prismatic battery. These batteriesbasically have a constitution similar to that shown in FIG. 6 and theycomprise a anode, a cathode, a separator including an electrolyte, abattery housing and a pair of terminals.

[0149] In FIGS. 8 and 9, reference numerals 401 (in FIG. 8) indicates ananode comprising an anode active material layer, reference numeral 501(in FIG. 9) an anode active material layer, reference 502 (in FIG. 9) ananode, each of reference numerals 403 (in FIG. 8) and 508 (in FIG. 9) acathode comprising a cathode active material layer, reference numeral503 (in FIG. 9) a cathode active material layer, each of referencenumerals 405 and 505 an anode cap (or an anode terminal), each ofreference numerals 406 and 506 a cathode can (or a cathode terminal),each of reference numerals 407 and 507 a separator with an electrolyte(or an electrolyte solution) retained therein, and each of referencenumerals 410 and 510 a gasket (or an insulating packing).

[0150] In FIG. 9, reference numeral 500 indicates an anode collector,reference numeral 504 indicates a cathode collector, reference numeral511 an insulating plate, and reference numeral 514 a safety vent.

[0151] Particularly, in the single-layer structure type flat batteryshown in FIG. 8, a stacked body comprising the cathode 403 comprisingthe cathode active material and the the anode 401 comprising the anodeactive material layer stacked through at least the separator 407 havingan electrolyte solution retained therein is housed in the cathode can406 on the cathode side. The anode side of the stacked body in thecathode can 406 is sealed by the anode cap 405 as the anode terminal andthe residual inside space of the cathode can 406 is packed by the gasket410 (comprising an insulating material).

[0152] In the spiral-wound cylindrical battery shown in FIG. 9, astacked body wounded in multiple about a predetermined axis is housed inthe cathode can 506 as the cathode terminal such that the side face anda given bottom face side of the stacked body are covered by the cathodecan 506, said stacked body comprising at least the separator 507 havingan electrolyte solution retained therein interposed between the cathode508 containing the cathode active material layer 503 formed on thecathode collector 504 and the anode 502 containing the anode activematerial layer 501 formed on the anode collector 500. In the uncoveredside of the cathode can 506, the anode cap as the anode terminal isinstalled. The residual inside space of the cathode can 506 is packed bythe gasket 510 (comprising an insulating material). The stackedelectrode body having the cylindrical structure is electrically isolatedfrom the anode cap side through the insulating plate 511. The anode 502is electrically connected to the anode cap 505 by means of the anodelead 512. Similarly, the cathode 508 is electrically connected to thecathode can 506 by means of the cathode lead 513. On the anode cap side,there is provided the safety vent 514 for adjusting the internalpressure of the battery. This safety vent can be utilized for extractingthe electrolyte solution to the outside as previously described.

[0153] The prismatic battery shown in FIG. 10 comprises a plurality ofunit cells integrated in parallel connection through a collector in abattery housing 609 having a capping, wherein each unit cell comprises aseparator 607 having an electrolyte solution retained therein interposedbetween an anode 601 comprising an anode active material and a cathode603 comprising a cathode active material. The anode 601 is electricallyconnected to an anode terminal 605, and the cathode 603 is electricallyconnected to a cathode terminal 606. The prismatic battery is providedwith a plurality of safety vents 614 at the capping of the batteryhousing 609.

[0154] In the following, description will be made of each batteryconstituent.

[0155] As the constituent of the gasket (410, 510), there can be used,for example, fluororesin, polyamide resin, polysulfone resin, or variousrubbers. The battery sealing is typically conducted by way of caulkingwith the use of the gasket in the case of the structure as shown in FIG.8 or 9. Besides this, it may be conducted by means of glass sealing,adhesive sealing, welding or soldering.

[0156] As the constituent of the insulating plate 511 shown in FIG. 9,there can be used organic resins and ceramics.

[0157] Now, for the enclosed type battery whose constituent componentsare recovered in the present invention, in the case of suchconfiguration as shown in FIG. 8 or 9, the electrode terminals, cathodecan and anode can serve respectively as a battery housing correspondingto the battery housing of said enclosed type battery in which respectivebattery components are housed. Particularly, in the case of theconfiguration shown in FIG. 8, the cathode can 406 and the anode cap 405serve respectively as a battery housing which functions also as anoutputting terminal. In the case of the configuration shown in FIG. 9,the cathode can 506 and the anode cap 505 serve respectively as abattery housing which functions also as a terminal. The constituent ofsuch battery housing functioning also as the terminal may be stainlesssteel, titanium clad stainless steel, copper clad stainless steel, ornickel-plated steel.

[0158] In the configurations shown in FIGS. 8 and 9, since the cathodecan (406, 506) and the anode cap (405, 505) function respectively alsoas a battery housing, they are desired to be constituted by stainlesssteel.

[0159] As in the case of such configuration as shown in FIG. 10, whenneither the cathode can nor the anode can functions also as a batteryhousing, the constituent of the battery housing can include metals suchas zinc, plastics such as polypropylene, and composites of a metal orglass fiber with plastic.

[0160] For the enclosed type battery whose constituent components arerecovered in the present invention, it is desired to be provided with anappropriate safety vent as in the case of the configuration shown inFIG. 9 (wherein the safety vent 514 is provided) or FIG. 10 (wherein thesafety vents 614 are provided) in order to ensure the safety when theinternal pressure of the battery is incidentally increased, bycommunicating the inside of the battery with the outside to therebyreduce the increased internal pressure of the battery. The safety ventmay be constituted by a material comprising a rubber, a spring, a metalboll or a rupture foil. The safety vent can be utilized for extractingthe electrolyte solution present in the battery as previously described.

[0161] In the following, description will be made of each of the anode,cathode, separator and electrolyte of the enclosed type battery used inthe present invention.

Anode

[0162] The enclosed type battery in which an aqueous electrolytesolution is used and whose constituent components are recovered in thepresent invention includes lead-acid battery, nickel-cadmium battery,nickel-metal hydride battery, and nickel-zinc battery.

[0163] The anode in these batteries comprises an anode active materialcomprising lead, cadmium, hydrogen-absorbing alloy or zinc, and an anodecollector.

[0164] The enclosed type battery whose constituent components arerecovered in the present invention also includes various lithiumbatteries. The anode in these lithium batteries comprises a principalconstituent which retains lithium therein at a stage before operatingdischarging, and an anode collector.

[0165] Specific examples of such principal constituent are lithiummetals, carbonous materials in which lithium is intercalated, transitionmetal oxides, and lithium alloys.

[0166] The anode collector serves to supply an electric current so thatit can be efficiently consumed for the electrode reaction upon operatingcharging and discharging or to collect an electric current generated.

[0167] The anode collector may be constituted by an appropriate materialwhich is highly electrically conductive and inactive to the batteryreaction.

[0168] Specific examples of such material are metals such as Ni, Ti, Cu,Al, Pt, Pd, Au, and Zn, alloys of these metals such as stainless steel,and composite metals of tow or more said metals.

[0169] The anode collector may be shaped in a plate-like form, foil-likeform, mesh form, porous form-like sponge, punching metal form, orexpanded metal form.

Cathoode

[0170] The cathode in the enclosed type battery whose constituentcomponents are recovered in the present invention generally comprises acathode collector, a cathode active material, an electrically conductiveauxiliary, and a binding agent.

[0171] The cathode is usually formed by disposing a mixture of a cathodeactive material, an electrically conductive auxiliary and a bindingagent on a member capable of serving as a cathode collector.

[0172] The electrically conductive auxiliary can include graphite,carbon blacks such as ketjen black and acetylene black, and metal finepowders of nickel or the like.

[0173] As the binding agent in the case of using a nonaqueous serieselectrolyte solution, there can be illustrated polyolefines such aspolyethylene, polypropylene, and the like; and fluororesins such aspolyvinylidene fluoride, tetrafluoroethylene polymer, and the like.

[0174] As the binding agent in the case of using an aqueous serieselectrolyte solution, there can be illustrated celluloses, polivinylalcohol, and polyvinyl chloride, in addition those illustrate in thecase of using the nonaqueous series electrolyte solution.

[0175] As the cathode active material in the enclosed type battery inwhich an aqueous series electrolyte solution is used and whoseconstituent components are recovered in the present invention such aslead-acid battery, nickel-cadmium battery, nickel-metal hydride battery,or nickel-zinc battery, there is used lead oxide, nickel (III)oxyhydroxide or nickel hydroxide.

[0176] The enclosed type battery whose constituent components arerecovered in the present invention includes also various lithiumbatteries. As the cathode active material in these lithium batteries,there is usually used a compound selected from transition metal oxides,transition metal sulfides, lithium-transition metal oxides, andlithium-transition metal sulfides. The metals of these transition metaloxides and transition metal sulfides can include metals partially havinga d-shell or f-shell. Specific examples of such metal are Sc, Y,lanthanoids, actinoids, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au. Of these, Ti, V, Cr,Mn, Fe, Co, Ni and Cu are particularly appropriate.

[0177] The cathode collector in the enclosed type battery whoseconstituent components are recovered in the present invention serves tosupply an electric current so that it can be efficiently consumed forthe electrode reaction upon conducting the charging and discharging orto collect an electric current generated. The cathode collector istherefore desired to be constituted by a material which has a highelectrical conductivity and is inactive to the battery reaction.

[0178] The material by which the cathode collector is constituted caninclude Ni, Ti, Cu, Al, Pt, Pb, Au, Zn, alloys of these metals such asstainless steel, and composite metals of two or more of said metals.

[0179] The cathode collector may be shaped in a plate-like form,foil-like form, mesh form, porous form-like sponge, punching metal form,or expanded metal form.

[0180] Herein, the term “active material” in the foregoing anode orcathode active material means a material which is involved in therepetition of electrochemical reversible reaction of charging anddischarging in the battery. Said active material can include, inaddition to said material which is involved in the above reaction byitself, other material capable of being involved in the above reaction.

Separator

[0181] The separator in the enclosed type battery whose constituentcomponents are recovered in the present invention is disposed betweenthe anode and the canthode, and it serves to prevent the anode and thecathode from suffering from internal-shorts. In addition, the separatoralso serves to retain the electrolyte solution.

[0182] The separator is required to have a porous structure capable ofallowing ions involved in the charge and discharge reaction in thebattery to pass therethrough and it is also required to be insolubleinto and stable to the electrolyte solution.

[0183] The separator is usually constituted by a nonwoven fabric or amemberane having a micropore structure made of glass, polyolefin such aspolypropylene or polyethylene, fluororesin, or polyamide. Alternatively,the separator may be constituted by a metal oxide film or a resin filmcombined with a metal oxide respectively having a number of micropores.

Electrolyte

[0184] For the electrolyte used in the enclosed type battery whoseconstituent components are recovered in the present invention, there canbe used an appropriate electrolyte as it is, a solution of saidelectrolyte dissolved in a solvent, or a material of said solutionhaving immobilized using a geling agent.

[0185] However, an electrolyte solution obtained by dissolving anappropriate electrolyte in an solvent is usually used in a way that saidelectrolyte solution is retained on the separator.

[0186] The higher the electrical conductivity of the electrolyte, thebetter. Particularly, it is desired to use such an electrolyte that theelectrical conductivity at 25° C. is preferably 1×10⁻³ S/cm or more ormore preferably, 5×10⁻³ S/cm or more.

[0187] In the case of a lead-acid battery, there is used an aqueoussolution of sulfuric acid as the electrolyte.

[0188] As the electrolyte in the case of a nickel-cadmium battery,nickel-metal hydride battery, or nickel-zinc battery, there is used anaqueous solution of an alkali. Particularly, there is usually used anaqueous solution of potassium hydroxide added with lithium hydroxided.

[0189] As the electrolyte in the case of a lithium battery, there isusually used a given electrolyte dissolved in a given solvent.

[0190] The electrolyte can include inorganic acids such as H₂SO₄, HCland HNO₃; salts of Li⁺(lithium ion) with Lewis acid ion such as BF₄ ⁻,PF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻, or BPh⁴ ⁻(with Ph being a phenyl group); andmixtures of two or more of said salts.

[0191] Besides these, salts of the above described Lewis acids ions withcations such as sodium ion, potassium ion, tetraalkylammonium ion, orthe like are also usable.

[0192] In any case, it is desired that the above salts are used afterthey are subjected to dehydration or deoxygenation, for example, by wayof heat treatment under reduced pressure.

[0193] The solvent in which the electrolyte is dissolved can includeacetonitrile, benzonitrile, propylene carbonate, ethylene carbonate,dimethyl carbonate, diethyl carbonate, dimethylformamide,tetrahydrofuran, nitrobenzene, dichloroethane, diethoxyethane,1,2-dimethoxyethane, chlorobenzene, γ-butyrolactone, dioxolan, sulfolan,nitrometane, dimethyl sulfide, dimethyl sulfoxide, methyl formate,3-methyl-2-oxdazolydinone, 2-methyltetrahydrofuran, 3-propylsydonone,sulfur dioxide, phosphonyl chloride, thionyl chloride, sulfuly chloride,and mixtures of two or more of these.

[0194] As for these solvents, it is desired for them to be subjected todehydration using activated alumina, molecular sieve, phosphorouspentaoxide, or calcium chloride, prior to their use. Alternatively, itis possible for them to be subjected to distillation in an atmospherecomposed of inert gas in the presence of an alkali metal, whereinmoisture and foreign matters are removed.

[0195] In order to prevent leakage of the electrolyte solution, it isdesired for the electrolyte solution to be gelated using an appropriategelating agent.

[0196] The gelating agent usable in this case can include polymershaving a property such that it absorbs the solvent of the electrolytesolution to swell. Specific examples of such polymer are polyethyleneoxide, polyvinyl alcohol, and polyacrylamide.

[0197] In the following, the present invention will be described in moredetail with reference to examples, which are only for illustrativepurposes but not intended to restrict the scope of the present inventionto these examples.

EXAMPLE 1

[0198] In this example, for a prismatic nickel-metal hydride batteryhaving the configuration shown in FIG. 10, based on the flow diagramshown in FIG. 1 and using the apparatus shown in FIG. 3 as a part of thepreviously described recovery system, the battery housing thereof wasunsealed, followed by subjecting to washing, the resultant wasdissociated into individual battery components, and these batterycomponents were separately recovered.

[0199] As the above battery, there was used a used prismaticnickel-metal hydride battery which comprises a cathode comprising aporous nickel material whose porous structure is filled by nickelhydroxide and nickel fine particles, an anode comprising a porous nickelmaterial whose porous structure is filled by a powdery hydrogen storagealloy and a binder, an electrolyte solution comprising an aqueoussolution of potassium hydroxide added with lithium hydroxide, and abattery housing made of polyopropylene.

[0200] In the following, the step of decreasing the ionic conductivityin the battery, the unsealing step, and the recovering step will besequentially explained with reference to FIGS. 1 and 3.

[0201] 1. A capacitor was electrically connected to the terminal of theprismatic nickel-metal hydride battery, followed by subjecting thebattery to discharging, whereby the residual electric capacity in thebattery was transferred into the capacitor.

[0202] 2. The battery thus discharged was set to the apparatus shown inFIG. 3 such that the safety vent-bearing face thereof was downward facedas shown in FIG. 3.

[0203] 3. By actuating the vacuum pump of the vacuuming means 105 andopening the exhaust valve 109, the inside of the storage tank 104 wasdepressurized, followed by closing the exhaust valve 109. Then, theswitching valve 108 was opened to actuate the safety vents of thebattery. By this, the internal pressure of the battery was increased andas a result, the electrolyte solution in the battery was extracted intothe extraction pipe 103, followed by flowing into the storage tank 104.Thereafter, the leak valve 113 was opened to introduce nitrogen gas intothe apparatus, whereby the inside of the storage tank 104 was returnedto atmospheric pressure. Then, the battery whose electrolyte solutionhaving been extracted was detached from the apparatus.

[0204] The electrolyte solution of the battery was recovered in thestorage tank 104. The electrolyte solution thus recovered can berecycled by filtrating and refining it.

[0205] 4. The battery whose electrolyte solution having been extractedobtained in the step 3 was set to a high pressure water cuttingapparatus, wherein a high pressure water (containing a powdery abrasive)of 3500 Kg/cm was sprayed onto the battery to cut and unseal the batteryhousing of the battery.

[0206] 5. From the unsealed battery obtained in the step 4, the cathode,anode and separator were taken out, washed, and dried, then followed byclassification and recovery.

[0207] In this case, because the electrolyte solution had been extractedfrom the battery in the step 3, even when the anode should have beencontacted with the cathode upon taking out them, they could be safelyrecovered with no energy release.

[0208] In the above, for the used prismatic nickel-metal hydride batterybefore the extraction of the electrolyte solution was conducted, theimpedance between the positive and negative terminals was measured bymeans of an impedance meter. As a result, it was found to be 2 mΩ. Andfor the used prismatic battery whose electrolyte solution having beenextracted, the impedance between the terminals was measured in the samemanner. As a result, it was found to be more than 5 MΩ. This indicatesthat by the above cooling, the internal resistance of the batteryseemingly has been desirably increased.

[0209] In this example, description has been made of the recovery of theprismatic nickel-metal hydride battery.

[0210] But the recovering manner of this example is not restrictive. Therecovering manner is effective in recovering other enclosed typebatteries in which a liquid electrolyte is used and having a safety ventsuch as nickel-cadmium battery, lead battery and lithium batteresincluding lithium ion battery.

EXAMPLE 2

[0211] In this example, for a cylindrical lithium battery having theconfiguration shown in FIG. 9, based on the flow diagram shown in FIG. 2and using the cooling and unsealing apparatus shown in FIG. 5, thebattery housing thereof was unsealed, followed by subjecting to washing,the resultant was dissociated into individual battery components, andthese battery components were separately recovered.

[0212] As the above battery, there was used a spent primary lithiumbattery in which a anode formed by press-laminating a lithium metal foilon an expanded metal of nickel, a cathode formed by applying a paste(obtained by mixing manganese dioxide (as a cathode active material),acetylene black (as an electrically conductive auxiliary) andpolyvinylidene fluoride (as a binder)) on a nickel mesh member anddrying the resultant, a separator comprising a polyethylene memberhaving a number of pores, and an electrolyte solution obtained bydissolving lithium tetrafluoroborate in an amount of 1M (mol/l) in amixed solvent composed of ethylene carbonate (EC) and dimethyl carbonate(DMC) are sealed by way of caulking. And there was used a stainlesssteel as the battery housing.

[0213] In the following, the step of discharging and recovering theresidual electric capacity in the battery prior to cooling the batteryin the flow diagram in FIG. 2, the step of cooling the battery, theunsealing step, and the recovering step will be sequentially explainedwith reference to FIGS. 2 and 5.

[0214] 1. A capacitor was electrically connected to the outputtingterminal of the used cylindrical primary lithium battery, followed bysubjecting the battery to discharging, whereby the residual electriccapacity in the battery was transferred into the capacitor.

[0215] 2. Using the cooling apparatus 201 in FIG. 5, the batterydischarged in the step 1 was immersed in a liquid nitrogen, followed bycooling the battery to a temperature lower than the coagulation point ofthe mixed organic solvent (composed of ethylene carbonate and dimethylcarbonate) of the electrolyte solution, whereby the ionic conductivityin the battery was decreased.

[0216] The impedances between the positive and negative terminals beforeand after the cooling treatment were measured by using the impedancemeter as in Example 1. The measured results revealed that the impedanceof before the cooling treatment is 60 mΩ and that after the coolingtreatment is more than 50 KΩ.

[0217] Besides, only for the only electrolyte solution, it was cooledunder the same condition as that for cooling the battery. And the ionicconductivities of the electrolyte before and after the coolingtreatment. As a result, the ionic conductivity before the coolingtreatment was found to seemingly have been decreased to {fraction(1/10)}by the cooling treatment.

[0218] 3. The battery cooled in the step 2 was taken out in an Ar gasatmosphere, it was mounted on the fixing table (207, in FIG. 5),followed by transporting by means of the transportation mechanism (208,in FIG. 5) to the unsealing zone containing the unsealing apparatus(204, in FIG. 5) comprising a high pressure water cutting apparatus,wherein an extra-high pressure water of 3500 Kg/cm² containing a powderyabrasive was sprayed onto the battery through the nozzle to cut andunseal the battery housing of the battery.

[0219] 4. The battery thus unsealed was subjected to washing withmethanol, where the active lithium present in the battery was convertedinto lithium alcoholate. Thereafter, the resultant mixed solventcomposed of the electrolyte solution and the methanol was recovered.From the cylindrical can as the battery housing, the anode, separatorand cathode were taken out and they were separately recovered.

EXAMPLE 3

[0220] In this example, for a coin-like shaped rechargeable lithiumbattery having the configuration shown in FIG. 8, based on the flowdiagram shown in FIG. 2 and using the cooling and unsealing apparatusshown in FIG. 5, the battery housing thereof was unsealed, followed bysubjecting to washing, the resultant was dissociated into individualbattery components, and these battery components were separatelyrecovered.

[0221] As the above battery, there was used a spent coin-like shapedrechargeable lithium battery in which a anode formed by press-laminatinga lithium metal foil on an expanded metal of nickel, a cathode formed byapplying a paste (obtained by mixing a lithium-nickel oxide material (asa cathode active material), acetylene black (as an electricallyconductive auxiliary) and polyvinylidene fluoride (as a binder) toobtain a mixture and and adding N-methylpyrrolidone to said mixture) ona nickel mesh member and drying the resultant, and a polymer solidelectrolyte obtained by dissolving lithium tetrafluoroborate in anamount of 1M (mol/1) in a mixed solvent composed of diethyl carbonateand propylene carbonate with an equivalent mixing ratio and solidifyingthe resultant by adding polyethylene oxide thereto are sealed by way ofcaulking. And there was used a stainless steel as the batter housing ofthe lithium battery.

[0222] In the following, the step of discharging and recovering theresidual electric capacity in the battery prior to cooling the batteryin the flow diagram in FIG. 2, the step of cooling the battery, theunsealing step, and the recovering step will be sequentially explainedwith reference to FIGS. 2 and 5.

[0223] As the cooling means (the cooling apparatus 201 in FIG. 5), therewas used a cooling apparatus (trademark name: VORTEX TUBE, produced byVORTEX Company of the United States) in which a compressed gas. As thecompressed gas, there was used CO₂ gas.

[0224] 1. CO₂ gas of 5 Kg/cm² was fed through the gas supply port of theforegoing cooling apparatus 201 to spray a CO₂ cold blast of −40° C.onto the used coin-like shaped rechargeable lithium battery, whereby thebattery was cooled to a temperature lower than the glass transitionpoint of the polyethylene oxide of the polymer solid electrolyte.

[0225] The impedances between the positive and negative terminals of theused battery before and after the cooling treatment were measured in thesame manner as in Example 1. The measured results revealed that theimpedance of before the cooling treatment is 500 mΩ and that after thecooling treatment is more than 5 MΩ. Based on this and the result of themeasurement of the ionic conductivities of the electrolyte solution inthe same manner as in Example 2, the ionic conductivity before thecooling treatment was found to seemingly have been decreased to{fraction (1/10)}as a result of the cooling treatment.

[0226] 2. The battery cooled in the step 2 was taken out in a CO₂ gasatmosphere, it was mounted on the fixing table (207, in FIG. 5),followed by transporting by means of the transportation mechanism (208,in FIG. 5) to the unsealing zone containing the unsealing apparatus(204, in FIG. 5) comprising a YAG laser cutting apparatus, wherein laserbeam was irradiated onto the battery to cut and unseal the batteryhousing of the battery.

[0227] 3. From the cut rechargeable battery can as the battery housing,the anode, polymer solid electrolyte and cathode were taken out and theywere separately recovered.

EXAMPLE 4

[0228] In this example, for a cylindrical rechargeable lithium batteryhaving the configuration shown in FIG. 9, based on the flow diagramshown in FIG. 2 and using the cooling and unsealing apparatus shown inFIG. 5, the battery housing thereof was unsealed, followed by subjectingto washing, the resultant was dissociated into individual batterycomponents, and these battery components were separately recovered.

[0229] As the above battery, there was used a used cylindricalrechargeable lithium battery in which a anode formed by applying a paste(obtained by mixing a natural graphite with polyvinylidene fluoride (asa binder) to obtain a mixture and adding N-methylpyrrolidone to saidmixture) on a copper foil and drying the resultant, a cathode formed byapplying a paste (obtained by mixing a lithium-cobalt oxide material (asa cathode active material), acetylene black (as an electricallyconductive auxiliary) and polyvinylidene fluoride (as a binder) toobtain a mixture and adding N-methylpyrrolidone to said mixture) on analuminum foil and drying the resultant, a separator comprising apolyethylene member having a number of pores, and an electrolytesolution obtained by dissolving lithium tetrafluoroborate in an amountof 1M (mol/l) in a mixed solvent composed of ethylene carbonate (EC) anddimethyl carbonate (DMC) with an equivalent mixing ratio are sealed byway of caulking. There was used a stainless steel as the battery housingof the battery.

[0230] In the following, the step of discharging and recovering theresidual electric capacity in the battery prior to cooling the batteryin the flow diagram in FIG. 2, the step of cooling the battery, theunsealing step, and the recovering step will be sequentially explainedwith reference to FIGS. 2 and 5.

[0231] As the cooling means (the cooling apparatus 201 in FIG. 5), therewas used a cooling apparatus (trademark name: VORTEX TUBE, produced byVORTEX Company of the United States) in which a compressed gas. As thecompressed gas, there was used Ar gas.

[0232] 1. A capacitor was electrically connected to the outputtingterminal of the cylindrical rechargeable lithium battery, followed bysubjecting the battery to discharging, whereby the residual electriccapacity in the battery was transferred into the capacitor.

[0233] 2. Ar gas of 7 Kg/cm² was fed through the gas supply port of theforegoing cooling apparatus 201 to spray an Ar cold blast of −30° C.onto the spent cylindrical rechargeable lithium battery discharged inthe step 1, whereby the battery was cooled to a temperature lower thanthe coaguration point of the mixed solvent (composed of the ethylenecarbonate and dimethyl carbonate) of the electrolyte solution.

[0234] The impedances between the positive and negative terminals beforeand after the cooling treatment were measured in the same manner as inExample 1. The measured results revealed that the impedance of beforethe cooling treatment is 80 mΩ and that after the cooling treatment ismore than 5 kΩ. Based on this and the result of the measurement of theionic conductivity of the electrolyte solution in the same manner as inExample 2, the ionic conductivity before the cooling treatment was foundto seemingly have been-decreased to {fraction (1/10)}as a result of thecooling treatment.

[0235] 3. The battery cooled in the step 2 was taken out in an Ar gasatmosphere, it was mounted on the fixing table (207, in FIG. 5),followed by transporting by means of the transportation mechanism (208,in FIG. 5) to the unsealing zone containing the unsealing apparatus(204, in FIG. 5) comprising an extra-high pressure cutting apparatus,wherein an extra-high pressure water (containing a powdery abrasive) of3500 Kg/cm² was sprayed onto the battery to cut and unseal the batteryhousing of the battery.

[0236] 4. The battery thus unsealed was subjected to washing with water,where the active lithium present in the battery was converted intolithium hydroxide. Thereafter, it was further washed, where theresultant mixed solvent composed of the electrolyte solution, methanoland water was recovered. From the cylindrical can as the batteryhousing, the anode, separator and cathode were taken out and they wereseparately recovered. The above mixed solvent composed of theelectrolyte solution, methanol and water was subjected to distillation,where the electrolyte, organic solvent and methanol were separatelyrecovered.

EXAMPLE 5

[0237] In this example, using a used cylindrical rechargeable lithiumbattery having the same constitution as that of the cylindricalrechargeable lithium battery used in Example 4 and based on the flowdiagram shown in FIG. 2, the battery housing thereof was unsealed,followed by subjecting to washing, the resultant was dissociated intoindividual battery components, and these battery components wereseparately recovered.

[0238] In the following, the step of discharging and recovering theresidual electric capacity in the battery prior to cooling the batteryin the flow diagram in FIG. 2, the step of cooling the battery, theunsealing step, and the recovering step will be sequentially explainedwith reference to FIG. 2.

[0239] 1. A capacitor was electrically connected to the outputtingterminal of the cylindrical rechargeable lithium battery, followed bysubjecting the battery to discharging, whereby the residual electriccapacity in the battery was transferred into the capacitor.

[0240] 2. The spent cylindrical rechargeable lithium battery dischargedin the step 1 was immersed in a vessel filled with water, followed bysubjecting to quick freezing, whereby the battery was sealed in an ice.

[0241] The impedances between the positive and negative terminals of theused battery before and after the cooling treatment were measured in thesame manner as in Example 1. The measured results revealed that theimpedance of before the cooling treatment is 80 mΩ and that after thecooling treatment is more than 3 kΩ. Based on this and the result of themeasurement of the ionic conductivity of the electrolyte solution in thesame manner as in Example 2, the ionic conductivity before the coolingtreatment was found to seemingly have been decreased to {fraction(1/10)}by the cooling treatment.

[0242] 3. The battery sealed in the ice in the step 2 was taken out in anitrogen gas atmosphere, it was mounted on a fixing table, followed bytransporting to a disk cutter capable of rotating at a high speed toconduct cutting for an object, where the battery sealed in the ice wascut whereby the battery housing of the battery was unsealed.

[0243] 4. The battery thus unsealed was thawed, followed by washing withacetone, where the resultant mixed solvent composed of the electrolytesolution, acetone and water was recovered. From the cylindrical can asthe battery housing, the anode, separator and cathode were taken out andthey were separately recovered. The above mixed solvent composed of theelectrolyte solution, acetone and water was subjected to distillation,where the electrolyte, organic solvent and methanol were separatelyrecovered.

EXAMPLE 6

[0244] In this example, for a prismatic rechargeable lithium batteryhaving the configuration shown in FIG. 10, based on the flow diagramshown in FIG. 2, the battery housing thereof was unsealed, followed bysubjecting to washing, the resultant was dissociated into individualbattery components, and these battery components were separatelyrecovered. Though not shown in FIG. 10, in said prismatic rechargeablelithium battery, a battery housing made of an aluminum alloy and abattery caping provided with a pair of outputting and inputtingterminals and a plurality of safety vents are assembled through anO-ring and with bises.

[0245] As the above battery, there was used a used prismaticrechargeable lithium battery in which a anode formed by applying a paste(obtained by mixing a natural graphite with polyvinylidene fluoride (asa binder) to obtain a mixture and adding N-methyl-2-pyrrolidone to saidmixture) on a copper foil and drying the resultant, a cathode formed byapplying a paste (obtained by mixing a lithium-cobalt oxide material (asa cathode active material), acetylene black (as an electricallyconductive auxiliary) and polyvinylidene fluoride (as a binder) toobtain a mixture and adding N-methylpyrrolidone to said mixture) on analuminum foil and drying the resultant, a separator comprising apolyethylene member having a number of pores, and an electrolytesolution obtained by dissolving lithium tetrafluoroborate in an amountof 1M (mol/l) in a mixed solvent composed of ethylene carbonate (EC) anddimethyl carbonate (DMC) with an equivalent mixing ratio are sealed, anda blade spring for pressing in order to shorten the distance between thecathode and anode is inserted.

[0246] In the following, the step of discharging and recovering theresidual electric capacity in the battery prior to cooling the batteryin the flow diagram in FIG. 2, the step of cooling the battery, theunsealing step, and the recovering step will be sequentially explainedwith reference to FIG. 2.

[0247] As the cooling means, there was used dryice-metahanol.

[0248] 1. A capacitor was electrically connected to the outputtingterminal of the prismatic rechargeable lithium battery, followed bysubjecting the battery to discharging, whereby the residual electriccapacity in the battery was transferred into the capacitor.

[0249] 2. The used prismatic rechargeable lithium battery discharged inthe step 1 was immersed in a dryice-methanol freezing agent obtained byadding a dryice to methanol, whereby the battery was cooled to atemperature lower than the coaguration point of the mixed solvent(composed of the ethylene carbonate and dimethyl carbonate) of theelectrolyte solution to decrease the ionic conductivity in the battery.

[0250] The impedances between the positive and negative terminals of thebattery before and after the cooling treatment were measured in the samemanner as in Example 1. The measured results revealed that the impedanceof before the cooling treatment is 70 mΩ and that after the coolingtreatment is more than 1 MΩ. Based on this and the result of themeasurement of the ionic conductivity of the electrolyte solution in thesame manner as in Example 2, the ionic conductivity before the coolingtreatment was found to seemingly have been decreased to {fraction(1/10)}as a result of the cooling treatment.

[0251] 3. The battery cooled in the step 2 was taken out in an Ar gasatmosphere, and the vises were loosen to detach the battery cappinghaving the safety vents, whereby the battery housing was unsealed.

[0252] 4. From the battery thus unsealed, the anode, separator, cathodeand blade spring were taken out, followed by subjecting to washing withmetanol, and the anode, separator, cathode, and blade spring and alsothe mixed solvent composed of the electrolyte solution and the methanolywere separately recovered. The mixed solution composed of theelectrolyte solution and methanol was subjected to distillation, wherethe electrolyte, organic solvent and methanol were separately recovered.

[0253] Incidentally, in each of the foregoing examples 2 to 6, therecovery operation was conducted for 10 batteries, where neither smokenor spark were occurred, the battery components were not damaged due toburning or the like and the battery components could be desirablyrecovered in any case.

[0254] In each of the foregoing examples 2 to 6, description has beenmade of the recovery of the enclosed type lithium battery. But therecovering manner of any of these examples is not restrictive. Therecovering manner described any of these examples is effective inrecovering other enclosed type batteries as nickel-metal hydridebattery, nickel-cadmium battery, lead battery and the like.

[0255] As above described, according to the present invention, for anyspent, enclosed type batteries, its constituent components can be moresafely recovered while desirably preventing them from being damaged andat a high recovery. And the recovering apparatus (system) enables torelatively easily recover the components of an enclosed type battery ata reasonable cost.

What is claimed is:
 1. A recovering process for recovering theconstituent components of a sealed type batter comprising at least an acathode, an anode and an electrolyte sealed in a battery housing,characterized in that said process includes a step (a) of decreasing theionic conductivity between said cathode and anode of said sealed typebattery and a step (b) of opening said battery housing of the sealedtype battery after conducting said step (a).
 2. A recovering processaccording to claim 1 , wherein the sealed type battery has anelectrolyte solution as the electrolyte between the anode and cathode,and the step (a) is conducted by extracting the electrolyte solution orthe solvent of the electrolyte solution outside the battery housing. 3.A recovering process according to claim 2 , wherein the sealed typebattery has a safety vent, and a differential pressure is caused betweenthe inside and outside of the battery housing to actuate said safetyvent, whereby extracting the electrolyte solution or the solvent of theelectrolyte solution through said safety vent outside the batteryhousing.
 4. A recovering process according to claim 3 , wherein aportion of the sealed type battery where the safety vent is provided ispositioned to face in a downward direction and the electrolyte solutionor the solvent of the electrolyte solution is extracted through thesafety vent outside the battery housing.
 5. A recovering processaccording to claim 2 , wherein the electrolyte solution or the solventof the electrolyte solution extracted outside the battery housing isrecovered.
 6. A recovering process according to claim 1 , wherein thestep (a) is conducted by at least cooling the sealed type battery.
 7. Arecovering process according to claim 6 , wherein the sealed typebattery has an electrolyte solution as the electrolyte between the anodeand cathode, and the sealed type battery is cooled to a temperaturelower than the freezing point of the solvent of the electrolytesolution.
 8. A recovering process according to claim 6 , wherein apolymer solid electrolyte solidified using a polymer is used in thesealed type battery, and the sealed type battery is cooled to atemperature lower than the glass transition temperature of the polymerof the polymer solid electrolyte.
 9. A recovering process according toclaim 6 , wherein the sealed type battery is cooled by using acompressed incombustible gas comprising one or more kinds of gasselected from the group consisting of nitrogen gas, argon gas, heliumgas, carbon dioxide gas and fluorocarbon gas.
 10. A recovering processaccording to claim 6 , wherein the sealed type battery is cooled byimmersing the sealed type battery in a cooling agent or liquefied gas.11. A recovering process according to claim 10 , wherein the coolingagent is a mixture of a dryice and methanol or a mixture of a dryice andethanol.
 12. A recovering process according to claim 10 , wherein theliquefied gas is liquid nitrogen.
 13. A recovering process according toclaim 6 , wherein the sealed type battery is immersed in water, thesealed type battery is frozen together with said water to seal thesealed type battery in an ice produced, and the sealed type battery isopened in a state in that the sealed type battery is sealed in the ice.14. A recovering process according to claim 1 , wherein the step (b) isconducted in an incombustible atmosphere.
 15. A recovering processaccording to claim 14 , wherein the incombustible atmosphere is composedof one or more kinds of gas selected from the group consisting ofnitrogen gas, argon gas, helium gas, carbon dioxide gas, steam andfluorocarbon gas.
 16. A recovering process according to claim 9 ,wherein the step (b) is conducted in an incombustible atmospherecomposed of the same gas as that used in cooling the sealed typebattery.
 17. A recovering process according to claim 1 , wherein thestep (b) is conducted by means of a cutting manner selected from thegroup consisting of high pressure water cutting, energy beam cutting andmechanical cutting.
 18. A recovering process according to claim 17 ,wherein the high pressure water cutting is a cutting manner of sprayinga high pressure water containing an abrasive through a jet nozzle.
 19. Arecovering process according to claim 17 , wherein the energy beam usedin the energy beam cutting is laser beam.
 20. A recovering processaccording to claim 1 , wherein the sealed type battery is a lithiumbattery in which oxidation-reduction reaction of lithium ion is used.21. A recovering process according to claim 1 , wherein the sealed typebattery is a nickel-metal hydride battery in which oxidation-reductionreaction of hydrogen ion is used and a hydrogen storage alloy is used asan anode material.
 22. A recovering process according to claim 1 ,wherein the sealed type battery is a nickel-cadmium battery.
 23. Arecovering process according to claim 1 , wherein the sealed typebattery is a lead-acid battery.
 24. A recovering process according toclaim 20 which further includes a step of reacting a reacting agent withan active lithium contained in the lithium battery to decrease thereactivity of said active lithium after the step (b).
 25. A recoveringprocess according to claim 24 , wherein the reacting agent comprises oneor more materials selected from the group consisting of water, alcohols,acids, and carbon dioxide.
 26. A recovering process according to claim20 which further includes a step of conducting washing the openedlithium battery with the use of an organic solvent which is conductedafter the step (b).
 27. A recovering process according to claim 26 ,wherein the organic solvent is an organic solvent incapable producing anazeotrope with water.
 28. A recovering process according to claim 26which further includes a step of dissociating the sealed type batteryinto individual battery components and recovering the constituentcomponents of the sealed type battery which is conducted after thewashing step with the use of the organic solvent.
 29. A recoveringprocess according to claim 1 , wherein the sealed type battery is sorteddepending on the shape or the type prior to the step (a).
 30. Arecovering process according to claim 1 which further includes a step ofdischarging the electric residual capacity of the sealed type batteryprior to conducting the step (a).
 31. A recovering process according toclaim 30 , wherein in the step of discharging the residual electriccapacity, an energy discharged is recovered.
 32. A recovering apparatusfor recovering the constituent components of a sealed type battercomprising at least an a cathode, an anode and an electrolyte housed ina battery housing, said apparatus comprising at least a means (i) fordecreasing the ionic conductivity between said cathode and anode of saidsealed type battery and a means (ii) for opening said battery housing.33. A recovering apparatus according to claim 32 , wherein the sealedtype batter comprises an electrolyte solution as the electrolyte betweenthe anode and cathode, and the means (i) comprises a liquid extractionmeans (i-a) for extracting the electrolyte solution or the solvent ofthe electrolyte solution outside the battery housing.
 34. A recoveringapparatus according to claim 33 , wherein the sealed type battery has acapping provided with a safety vent, and the liquid extraction means(i-a) includes a means (i-b) for causing a differential pressure betweenthe inside and outside of the battery housing through said safety ventto actuate said safety vent whereby extracting the electrolyte solutionor the solvent of the electrolyte solution outside the battery housing.35. A recovering apparatus according to claim 34 , wherein the means(i-b) comprises at least a vessel (i-c) capable of being vacuumed andwhich is provided with an exhausting means.
 36. A recovering apparatusaccording to claim 35 , wherein the vessel (i-c) has a member capable oftightly contacting or joining with an exterior wall face portion of thebattery housing of the sealed type battery, said exterior wall faceportion comprising a portion of the capping, said portion including theneighborhood of the safety bent, and said member having an openingthrough which said exterior wall face portion is communicated with thevessel (i-c) so that the electrolyte solution or the solvent thereof inthe sealed type battery is capable of being extracted through saidmember into the vessel (i-c).
 37. A recovering apparatus according toclaim 35 , wherein a passage capable of introducing air, nitrogen gas orinert gas is provided at the vessel (i-c) through a valve.
 38. Arecovering apparatus according to claim 34 , wherein a closed spacecomprising a part or the entire of an exterior wall face of the batteryhousing including the neighborhood of the safety vent and the vessel(i-c) is formed such that the safety vent is situated within said closedspace and that the internal pressure of said closed space is capable ofbeing decreased to be lower than that of the sealed type battery,wherein the electrolyte solution or the solvent thereof in the sealedtype battery is capable of being extracted into said closed space.
 39. Arecovering apparatus according to claim 38 , wherein the closed space isestablished after the internal pressure of the vessel (i-c) is decreasedto be lower than the atmospheric pressure by means of an exhaustingmeans.
 40. A recovering apparatus according to claim 38 , wherein afterthe closed space is formed, the internal pressure of the closed space isdecreased to be lower than that of the sealed type battery by means ofan exhausting means connected to the vessel (i-c).
 41. A recoveringapparatus according to claim 32 , wherein the means (i) comprises atleast a means (i-d) for cooling the sealed type battery.
 42. Arecovering apparatus according to claim 41 , wherein the cooling means(i-d) is for freazing the sealed type battery to a temperature lowerthan the freezing point of the solvent of the electrolyte solution. 43.A recovering apparatus according to claim 41 , wherein a polymer solidelectrolyte solidified by a polymer is used as the electrolyte in thesealed type battery, and the cooling means (i-d) for cooling the sealedtype battery to a temperature lower than the glass transitiontemperature of the polymer of the polymer solid electrolyte.
 44. Arecovering apparatus according to claim 41 , wherein a compressedincombustible gas comprising one or more kinds of gas selected from thegroup consisting of nitrogen gas, argon gas, helium gas, carbon dioxidegas and fluorocarbon gas is used in the cooling means (i-d).
 45. Arecovering apparatus according to claim 41 , a cooling agent orliquefied gas is used in the cooling means (i-d).
 46. A recoveringapparatus according to claim 45 , wherein the cooling agent is a mixtureof a dryice and methanol or a mixture of a dryice and ethanol.
 47. Arecovering apparatus according to claim 45 , wherein the liquefied gasis liquid nitrogen.
 48. A recovering apparatus according to claim 41 ,wherein the cooling means (i-d) is for immersing the sealed type batteryin water and freezing the enclosed type battery together with said waterto seal the sealed type battery in an ice produced, and the openingmeans (ii) is for opening the sealed type battery sealed in the ice. 49.A recovering apparatus according to claim 32 , wherein the opening means(ii) includes a means capable of making the atmosphere in which to openthe sealed battery is conducted by means of the opening means (ii) to bean incombustible atmosphere.
 50. A recovering apparatus according toclaim 49 , wherein the incombustible atmosphere is composed of one ormore kinds of gas selected from the group consisting of nitrogen gas,argon gas, helium gas, carbon dioxide gas, steam and fluorocarbon gas.51. A recovering apparatus according to claim 50 , wherein the sealedtype battery is opened by means of the opening means (ii) in anincombustible atmosphere composed of the same gas as that used incooling the sealed type battery by means of the cooling means (i-d). 52.A recovering apparatus according to claim 32 , wherein the opening means(ii) comprises a cutting means selected from the group consisting ofhigh pressure water cutting, energy beam cutting and mechanical cutting.53. A recovering apparatus according to claim 52 , wherein the highpressure water cutting means comprises a jet nozzle and is a cuttingmeans for spraying a high pressure water containing an abrasive throughthe jet nozzle.
 54. A recovering apparatus according to claim 52 ,wherein the energy beam used in the energy beam cutting is laser beam.55. A recovering apparatus according to claim 32 , wherein the sealedtype battery is a lithium battery in which oxidation-reduction reactionof lithium ion is used.
 56. A recovering apparatus according to claim 32, wherein the sealed type battery is a nickel-metal hydride battery inwhich oxidation-reduction reaction of hydrogen ion is used and ahydrogen alloy is used as anode material.
 57. A recovering apparatusaccording to claim 32 , wherein the sealed type battery is anickel-cadmium battery.
 58. A recovering apparatus according to claim 32, wherein the sealed type battery is a lead-acid battery.
 59. Arecovering apparatus according to claim 55 which further includes ameans for reacting a reacting agent with an active lithium contained inthe lithium battery to decrease the reactivity of said active lithiumafter the lithium battery is opened.
 60. A recovering apparatusaccording to claim 59 , wherein the reacting agent comprises one or morematerials selected from the group consisting of water, alcohols, acids,and carbon dioxide.
 61. A recovering apparatus according to claim 32which further comprises a means for conducting washing with the use ofan organic solvent after the sealed type battery is opened.
 62. Arecovering apparatus according to claim 61 , wherein the organic solventis an organic solvent incapable producing an azeotrope with water.
 63. Arecovering apparatus according to claim 61 or 62 which further comprisesa means for recovering the constituent battery components after washingthe opened battery with the use of the organic solvent.
 64. A recoveringapparatus according to claim 32 which further comprising a means forsorting the sealed type battery depending on the shape or the type priorto cooling said sealed type battery.
 65. A recovering apparatusaccording to claim 32 which further comprises a means for dischargingthe electric residual capacity of the sealed type battery prior tocooling said battery.
 66. A recovering apparatus according to claim 65 ,wherein the discharging means includes a means recovering an energydischarged.
 67. A recovering apparatus according to claim 50 whichfurther comprises a means for recovering the incombustible gas of theopening atmosphere and purifying the incombustible gas recovered torecycle.
 68. A recovering apparatus according to claim 44 which furthercomprises a means for recovering the gas used in cooling the sealed typebattery and purifying the gas recovered to recycle.